Synthetic drx



Patented Apr. 13, 1937 UNITED STATES SYNTHETIC OIL BODIES Alfred E. Rhcineck and Rabin, Louisville, Ky., and James 8. Long. Coopcrsburg, Pa" assignors to Devon & Raynolds 00., Inc., a-cornotation of New York No Drawing. Application January 21, 1985 Serial No. 2,752

13 China.

This invention relates to the production of synthetic esters of fatty acids derived from natural drying oils. all of which acids have at least 16 carbon atoms.

Under this invention products of a great variety of natures can be produced by combining together various fatty acids in proportions not found in nature, or by combining various types. or by uniting various fatty acids with many different types of organic bases which, like the polyhydric alcohols and the sugars, are adapted to be esterifleci.

A particular phase of the invention relates to the production of esters comprising a plurality of fatty acid radicals with the molecules comprising acid chains having conjugate double bonds and also poly-unsaturated acid chains not having such conjugate double bonds. monly found natural oil containing conjugate double bonds is China-wood oil. Another oil also containing conjugate double bonds is oiticica. and for the purpose of this application such oils are generally referred to as conjugated" oils and the poly-unsaturated components of their acids are referred to as "conjugated fatty acids".

China-wood oii'is recognized as having many highly valuable qualities but it also creates certain difllcuities. For example, it gels easily in the kettle when heated and if used without first being heat-bodied to some extent it dries or sets to a frosted film. Various expedients have been tried for overcoming this difliculty, but all the attempts heretofore tried have been subject to more or less criticism. I We have found that it is possible to obtain products having the advantageous qualities of the China-wood oil compounds but free from most of their defects by making up synthetic bodies in which the characteristic conjugated fatty acids such as those found in China-wood oil are combined chemically in a single molecule with other bodies of a type adapted for use in film-forming compounds but having distinctly diii'erent characteristics from the conjugated fatty acids. The 5 simplest illustration of such a synthetic body is a tri-glycerlde consisting of molecules each comprising at least one conjugated fatty acid chain and at least one poly-unsaturated but non-conjugated acid chain. The third chain may be of V either type as desired though we have usually found it advantageous to use two of the conjugated chains and one of the non-conjugated chains. Such a product can be made by mixing toge'her the fatty acids of a conjugated oil such as China-wood oil and the fatty acids anon- The most comconjugated drying oil such as linseed oil or soy bean oil or fish oils or any 01' the other wellknown types, and causing them to combine with glycerine by known processes'such as heating while removing water of condensation by passing a stream 01' inert gas through the liquid. This process produces products of value but these products can be materially improved if the fatty acids are first treated to reduce the content of saturated or mono-unsaturated acids. This may 10 be done, with China-wood acids, for example, by dissolving the acids in hot alcohol which is subsequently chilled. The desired acids, eleostearic or enriched China-wood oil acids, separate out, and after filtration, progressive removal of the 1 desired acids can be had by repeated evaporation and chilling of the solution. By using this intermediate treatment the drying qualities of the final product are appreciably improved. This concentrating step is particularly valuable with go the conjugated oil acids.

instead of mixing the fatty acids the esteriflcation can be conducted in steps. In this connection we have found that there is a natural tendency to form the di-glyceride as evidenced by the 25 fact that if less than two molecules of acid are used for each molecule of glycerlne a substantial percentage of uncombined glycerine will separate out on standing. This permits of a method of. control whereby we can be assured of having 30 substantially an oil comprising two of the conjugated acid radicals and one of the non-con- Jugated acid radicals to each molecule, for we can first treat the glycerine with a, suilicient quantity of eleostearic acid to produce the di- .35

giyceride and finally add the other poly-unsaturated non-conjugated acid.

In addition to the production of tri-glycerldes oi the fatty acids, our invention can also be applied to the production ofmany other interest- 4 ing products. We have found, for example, that in producing synthetic esters of the polyhydric alcohols by the combination of the acids of drying pils, the product has improved drying qualities somewhat in proportion to the increase in 45 the number of acid chains which are combined in a secondary position. Thus we have found that the drying oil acid esters of erythritol (CHQDH(CHOH)2CH2OH) has better qualities than the corresponding ester of the same fatty acid with penta erythritol (C(CHaOHh). Further, the corresponding ester of mannitol (which is intended to include sorbitoi) has better drying qualities than the corresponding ester of erythritol. These products have distinctly valu- 2 able characteristics-even whenno conjugated acid is used, and the compounds which include the radicals of the China-wood oil acids are of especial merit.

5 Conversely we have found that an ester of ethylene glycol where none of the acid chains will be in the secondary position has less hardening characteristic so that a plasticizer of value can be obtained by combining with the ethylene 10 glycol molecule one molecule of eleostearic acid from China-wood oil and one molecule of another type of fatty acid derived from either a drying oil or a non-drying oil such as castor oil. The resulting product oxidizes but does not dry 15 or set hard but remains somewhat plastic and being compatible with the films of paints and varnishes can readily be incorporated as plasticizers for these products. The proportion of such mixed ethylene glycol esters found desirable 20 in paint and varnish films may range from about 2% to about 20% of the weight of the nonvolatile vehicle.

In addition to the combination of the drying oil acids with the polyhydric alcohols it is also 25 within the spirit of our invention to cause these acids to combine with other related organic bases comprising a plurality of hydroxyl groups. Thus we have made many valuable products by building up moleculescomprising conjugated acid radicals and other poly-unsaturated drying oil'acid radicals and one of the sugars such as xylose, glucose, sucrose, dextrose, galactose, maltose, and fructose and also derivatives of sugars such as glu'conic acid and related bodies 5 such as simple glucosides, mannosides, and other ethers. Also if desired the acids of the blown drying oils may be used.

The production of the esters built around a sugar molecule is not possible by direct esterificantion. For making these products (and also in some instances for making the esters of the polyhydric alcohols) we find it advantageous first to produce the acid chlorides of the fatty acids and then cause the desired combination 5 to take place. To accomplish th s combination it is advisable as known, to have present a basic material which will combine with the released hydrochloric acid. For this purpose, we may use the cyclic tertiary amines such as pyridine or other organic bases may under some circumstances be used much as di-methyl aniline, and quinoline. I

According to our invention, we have also combined in a single molecule the poly-unsaturated 5 fatty acid radicals and other bodies having valuable film-forming characteristics, in particular the acid radicals of natural resins. Thus, we have made triple glycerides of conjugated fatty acid, other non-conjugated fatty acids and the acids of ordinary rosin or copals, the resulting product being a homogeneous mass, not a. mixture, adapted to be used as a varnish with or without the addition of diluent.

Using the glyceride base the proportions of the other ingredients are more or less limited if the mass is to be kept homogeneous, but this is'not the case with the alcohols having a greater number of hydroxyl .groups or with the sugars, where wide ranges in proportions of the various acid radicals are possible. In this connection,

we may point out that where a relatively high proportion of the conjugated fatty acid radicals are to be added as acid chlorides, it is advisable to use a diluting solvent. Such a solvent may a i also be used with other types of poly-unsaturated fatty acids but its use is not then so essential. Among the solvents which we have found useful for this purpose are isopropyl ether,

chloroform, benzene, and toluene.

In order further to explain our invention we give a number of specific examples. In these, where ,acid chlorides are used they were prepared by treating the respective fatty acids with phosphorous trichloride. After standing at room temperature for one hour, and then heating at 100 C. for one hour, two layers separate. The clear liquid, which is the acid chloride mixture, was then poured off from the underlying brown layer. The acid chlorides are next freed from hydrochloric acid by passing a stream of gas, e. g., carbon dioxide, through the warm product, until the issuing vapors no longer turn white in the presence of moisture. Various other methods of preparing acid chlorides involving phosphorus penta chloride, phosphorus oxychloride, thionyl chloride and others are known in the art and need not be here explained.

Example 1 The following is an example of an oil prepared by the esterification of sucrose with China-wood acid chlorides and perilla acid chlorides in the presence of pyridine and benzene.

Parts Sucrose 34.2 China-wood acid chlorides 6(1 Perilla acid chlorides 180 Pyridine 96 Benze 4.... 800

Mix the finely powdered sucrose, China-wood acid chlorides, perilla acid chlorides, and benzene, and while agitating vigorously, add the pyridine over a period of an hour. The temperature will rise to about 40 C. Pour the reaction product into an equal volume of methyl alcohol. Wash the oil which separates several times with hot methyl alcohol. Drive oil the excess alcohol by heating below 100 C. and passing through it a stream of carbon dioxide.

The resulting product is a viscous brownish yellow oil, which sets to a very tough non-frosting water-resistant film. It dries much more rapidly than natural drying oils, e. g., linseed, perilla, etc.

Other similar examples were run in which the China-wood acid chlorides ranged up to as much as 208 parts with a proportionate reduction of the perilla acid chlorides. In some cases the benzene was reduced to about 240 parts. Even with the high proportion of China-wood oil acids the resulting oil dried to a clear, non-frosting Example 2 The following is an example of an oil prepared by the esterification of dextrose and China-wood I acid chlorides and linseed acid chlorides.

Parts Dextrose 18 China-wood acid chlorides 50 Linseed acid chlorides 100 Pyridine 40 Benzene, 100

Mix the dextrose, the acid chlorides, and benzene and to this mixture add the pyridine while stirring. Pour the reaction mixture into an equal volume of methyl alcohol. Wash the oily layer with methyl alcohol several times until practically free from acid. Dry the oil by heating below This example describes the preparation of an oil from dextrose, China-wood acid chlorides and perilla acid chlorides.

. r Parts Dextrose 18 China-wood acid chlorides 110 Perilla acid chlorides 40 Pyridine 40 Benzene 200 Mix the dextrose, China-wood acid chlorides,

" perilla .acid chlorides, and 100 parts of benzene.

To this mixture add while stirring a mixture of pyridine and 100 parts of benzene. Purify the resulting oil as described in Example 2.

Example 4 This is an example of a dextrose ester having wood acid residues.

. Parts Dextrose 18 China-wood acid chlorides 150 Pyridine '40 Benzene e 200 This oil was prepared and purified exactly as described in Example 2. The product was an r amber colored, viscous liquid. It dried to a soft frosting film.

Example 5 The following is an example of an oil made by condensing mannitol with China-wood acid chlorides and sardine oil acid chlorides.

Parts Mannitol i 18.2 China-wood acid chlorides 114 Sardine oil acid chlorides 69 Pyridine 48 Benzene 120 The oil was prepared and purified in the same manner as the oil of Example 2. With driers it sets to a firm, water-resisting non-frosting film.

') Example 6 The following is an example of an oil prepared by condensing pentaerythritol with China-wood acid chlorides and sunflower acid chlorides. o5

This oil was prepared and purified in exactly the same manner as described in Example 2. The oil is a light-amber colored liquid.

Example 7 This is an example of a mixed ester of glycerol with equal parts of China-wood and perilla acid residues.

Parts Glycerol 9.2 China-wood acid chlorides 45 Perilla acid chlorides 45 Pyridine 24 enzene 60 all the hydroxyl groups condensed with China- This all also was prepared in the same manner as that of Example 2. It is a pale fairly fiuid oil. In another case 00 parts of China-wood acid chlorides were used with parts of linseed acid chlorides.

. Example 8 The following is an example of an oil prepared by direct esterification of glycerol with mixed China-wood linseed and rosin acids (abietic acid).

Parts Glycerol 92 Chinaw0od fatty acids 280 Linseed oil fatty acids 280 Abietic acid 302 Agitate and heat the reactants .at approximately 210 C. until the desired acid value is obtained. Benerally less than 10. This usually requires about 10 h0urs, but can be shortened if higher temperatures are used; however, the tendency for gel formation is increased; during the process a stream of carbon-dioxide is passed through the mixture.

The resulting viscous oil sets to a tough, tenacious, and non-frosting film, with drier. This product is thermoplastic.

It is soluble in the usual varnish thinners.

Example 9 The following is an example of the preparation of a mixture of monoglycerides and diglycerides of perilla fatty acids.

Parts Glycerol- 92 Perilla fatty acids 280 Follow the method outlined in Example 8. The time required to reach a negligible acid value is about four hours. Not all of the glycerol is esterifled, and can easily be separated from the esters.

The product so obtained is a mixture and one batch gave the following composition on analysis.

Percent Mono-glyceride 47 Di-glyceride 53 Example 10 The following is an example of an oil prepared by the further esterification of a mixture of a monoand di-glycerides of perilla fatty acids with China-wood oil fatty acids.

, Parts Glyceride (prepared in 47% Mono-l 500 Example 9) 53% Di- F" China-wood oil fatty acids 527 Mix the monoand di-g-lycerides with the fatty acids and heat as described in Example 8. until the acid value is reduced to a low value (1.7). This required 3% hours.

The resulting product is very light in color and possesses a high viscosity. It sets to a tough, permanent, non-frosting film in two hours. when the normal drier content is used.

v Example 11 The following is an example of an oil prepared by further esterification of a mixture of monoand di-glycerides of linseed oil fatty acids with China-wood oil acid chlorides in the presence of pyridine.

' Parts Glyceride of linseed fatty {53.9% Monofl 66 acids 46.1% Di- 1' China-wood acid chlorides 7&5 Pyridine 2O Benzene -r 20 75 Pyridine The following is an example of an oil prepared by the condensation of ethylene glycol with eleostearic acid chloride and. perilla acid chlorides in the presence of pyridine.

Parts Ethylene glycol 3.1 Eleostearicracid chloride 29.8 Perilla acid chloride 29.8 Pyridine 18 Agitate the ethylene glycol with the acid chlorides and add the pyridine gradually over a period of thirty minutes. The reaction mixture becomes thick and creamy. Pour the mixture into methyl alcohol, and pour off the alcohol from the insoluble layer. Washseveral times with methyl alcohol to remove free acids.

The product is a brown viscous oil which apparently remains tough and elastic after drying and is adapted for use as a plasticizer.

Example 13 The following is an example of an oil prepared by the condensation of glycerol with the mixed acid chlorides of China-Wood, perilla and rosin acids in benzene solution in the presence of pyridine.

Parts Glycerol 92 China-wood acid chlorides 298 Perilla acid chlorides 298 Rosin acid chlorides 320 Benzene 900 v Pyridine 240 'Agitate the glycerol and acid chlorides in about one-half the quantity of benzene, and then add the pyridine, diluted with the remaining benzene, in a slow stream over a period of thirty minutes. The solution becomes thick and creamy; after standing for another thirty minutes, pour the mass into methyl alcohol; a tough stringy mass separates. After several washings with methyl alcohol, a light colored viscous, clear oil separates. Several washings with the alcohol remove the free acid.

The oil sets to a tough clear film.

Emample 14 The following is an example of an oil prepared by the condensation of pentaerythritol with rosin acid chlorides, China-wood acid chlorides" and soya bean acid chlorides in benzene solution in the presence of pyridine. This corresponds to about a fifteen gallon varnish.

} Parts 70 Pentaerythritol 13.6 Soya bean acid chlorides 29.8 China-wood acid chlorides 29.8 Rosin acid chlorides 64.0 Benvene 120 35 Follow the method outlined in Example 13. The product possessed a very light color, was somewhat opaque, and very viscous. It set to a tough film.

Eazample 15 The following is an example of an oil prepared by the condensation of mannitol with rosin;

perilla, and China-wood acid chlorides in benzene solution in the presence of pyridine. Parts Mannitol 18.2 China-wood acid chlorides 59.6 Perilla acid chlorides"; 59.6 Rosin acid chlorides 64.0 Benzene 180. Pyridine 50 Follow the method outlined in Example 13. The product recovered is a clear dark colored viscous oil. It set to a tough film.

Example 16 The following is an example of an oil prepared by the condensation of dextrose with rosin, Chinawood, and linseed acid chlorides in benzene solution in the presence of pyridine.

Parts Dextrose 18.0 China-wood. acid chlorides 59.6 Linseed acid chlorides 29.8 Rosin acid chlorides 64.0 Benzene 150.0 Pyridine 40.0

Follow the method .outlined in Example 13. The product formed was a light colored, clear, viscous liquid, and set to a tough clear film.

Example 17 The following is an example of an oil prepared by the condensation of sucrose with rosin, China-wood and linseed fatty acid chlorides in benzene solution in the presence of pyridine. This corresponds to about a fourteen gallon varnish.

Parts Sucrose 34.2 Rosin acid chlorides 128.0 China-wood acid chlorides 98.4 Linseed acid chlorides 29.8 Benzene 250 Pyridine 70 Follow the method outlined in Example 13. The product is a light yellow colored, somewhat opaquc. viscous oil. It sets to a tough clear film.

Example 18 The following is an example of an oil prepared by the condensation of maltose with rosin, soya been. linseed and China-wood acid chlorides in benzene solution in the presence of pyridine.

, Parts Maltose 36.0 Soya bean acid chlorides 59.6 Linseed acid chlorides 89.4 Rosin acid chlorides 32.0 China-wood acid chlorides 59.6 Benzene 250.0 Pyridine 70.0

Follow the method outlined in Example 13. The product is a clear, dark colored, viscous oil which set to a tough film.

Example 19 The following is an example of an oil prepared by the esterification of alpha methyl glucoside with China-wood acid chlorides and linseed acid chlorides.

Parts Alpha. methyl glucoside 21.2 China-wood acid chlorides 90.0 Linseed acid chlorides 90.0 Benzene 90.0 Pyridine 50.0

Example The following is an example of an oil prepared by condensing dextrose with the acid chlorides made from blown linseed acids.

Parts Dextrose 18 Blown linseed acid chlorides 150 Pyridine 40 The blown linseed acids used in this example were prepared by blowing through a stream of air through the linseed acids for 12 hours at 50 C. The blown acids were subsequently treated with PCls to produce the acid chloride as described previously. To a mixture of the finely pulverized dextrose and the blown linseed acid chloride add the pyridine slowly and with vigorous agitation. Wash the resulting oil with water and then several times with methyl alcohol. Drive off the residual water and methyl alcohol by heating below 100 C. and blowing through it a stream of carbon dioxide.

The product is a dark colored viscous oil which sets to a clear tough film.

Escample 21 The following is an example of an oil prepared by the esterification of gluconic acid with perilla oil acid chloride.

Parts Gluconic acid 19.6 Perilla acid chlorides 130.0 P ridine--. 50.0

The gluconic acid and acid chlorides were mixed and the pyridine added slowly over a period of an hour. The creamy mass was poured into methyl alcohol. An oily mass, light yellow in color, separated. The product was washed severaltimes with methyl alcohol.

It sets to a tough film with the usual driers.

It is understood that these examples are given only by way of illustration and may be modifled greatly and the steps may be combined in other combinations without departing from the spirit of our invention.

What we claim is:

l. The process of producing film-forming compounds which comprises causing an organic base having a plurality of hydroxyl groups to combine with acid radicals of a co jugated drying oil acid and of a non-conjugated poly-unsaturated drying oil acid.

2. A process as specified in claim 1, in which said base is a polyhydric alcohol having at least two hydroxyl groups in the secondary position.

3. A process as specified in claim 1, in which said organic base is a sugar.

' 4. A process as specified in claim 1, in which said organic base is a mono-saccharide.

5. A process as specified in claim 1, in which an acid radical derived from a natural resin is also caused to re-combine with said organic base to form a composite ester comprising at least three types of acid radical.

6. A process as specified in claim 1, in which the organic base is caused first to combine with acid radicals of a conjugated fatty acid present in suflicient quantity to supply at least approximately two such acid radicals for each molecule of the base.

7. The method of producing a plasticizer for use in film-forming compounds and the like which comprises causing ethylene glycol to react witheleostearic acid and with a natural fatty acid of a diiferent type to produce a double ester thereof.

8. A drying oil consisting essentially of a compound ester of a polyhydric organic base, a drying oil acid having conjugate double bonds and a poly-unsaturated drying oil acid not having such conjugate double bonds.

9. A product as specified in claim 8'which comprises more than three acid radicals.

10. A product as specified in claim 8, in which at least one-half of the acid chains contain such conjugate double bonds.

11. A product as specified in claim 8, in which at least two of the drying oil acid radicals are combined in secondary positions.

12. A product as specified in claim 8, in which such ester further includes acid radicals of resin acids.

13. A drying oil consisting essentially of an ester of a sugar and the acid radicals of a blown drying oil.

ALFRED E. RHEINECK. BENJAMIN RABlN. JAMES 8. LONG. 

